Ink jet ink composition for textile printing, ink set, and recording method

ABSTRACT

An ink jet ink composition for textile printing including a dye and 5% to 30% by mass of a cyclic amide that is liquid at normal temperature and that has a normal boiling point in the range of 190° C. to 260° C., wherein the hue angle ∠h° defined by the CIELAB color space on a recording medium ranges from 15 to 80 degrees.

BACKGROUND 1. Technical Field

The present invention relates to an ink jet ink composition for textileprinting, an ink set, and a recording method.

2. Related Art

An ink jet recording method includes ejecting ink droplets from a finenozzle to deposit the ink droplets on a recording medium. This methodcan record high-resolution and high-quality images at high speed with arelatively inexpensive apparatus. The ink jet recording method requiresnumerous considerations, such as the properties of inks to be used,recording stability, and image quality. Thus, not only ink jet recordingapparatuses but also ink compositions to be used are extensivelystudied.

The ink jet recording method is also used for dyeing (textile printing)of textiles. Textiles (woven fabrics and nonwoven fabrics) have beenprinted by a screen textile printing method or a roller textile printingmethod. Due to the advantages of high-mix low-volume production andimmediate printing, however, the ink jet recording method is studied.

Ink compositions for use in textile printing ink jet recording alsorequire various performance characteristics. For dyeing of textiles,there is some demand for performance characteristics that are differentfrom those of general ink compositions. Thus, ink jet ink compositionsfor textile printing also require many considerations.

For example, reactive groups that react in textile printing maydeteriorate during storage. JP-A-2002-241639 discloses a liquidcomposition containing a monochlorotriazine reactive dye andtris(hydroxymethyl)aminomethane in order to achieve high temporalstability (storage stability) without significant decomposition ofreactive groups that react in textile printing.

An ink set composed of four dye inks of yellow, magenta, cyan, and black(YMCK) is also often used in ink jet textile printing. However, the useof such an ink set in the ink jet textile printing method sometimescannot accurately reproduce the hue range of the screen textile printingmethod. For example, a reactive dye ink set for ink jet textile printingis proposed in International Publication No. WO 2010/013649 in order toexpand the color reproduction range, particularly the color reproductionrange in the hue range of magenta-violet-blue-cyan. The reactive dye inkset includes a cyan ink composition containing C.I. Reactive Blue 15:1and a magenta ink composition containing C.I. Reactive Red 245.

As seen in these patent literatures, ink jet textile printing requireshigher storage stability of inks and a broader color reproduction rangeof printed textiles. Like inks for use in general ink jet recording,improved color developability of inks and printed textiles (alsoreferred to as printed matter or recorded matter) and higher imagerobustness (light fastness, etc.) of printed textiles are also required.

The present inventors have extensively studied the color developabilityand hue changes in ink jet textile printing in long-term outdoorexposure tests of printed textiles and have found that a particular huecreated by color mixing (hereinafter also referred to as composite) ofdifferent color inks, such as CMYK, is likely to change over time. Inparticular, long-term outdoor exposure tests of printed textiles showthat the hues of brown colors (colors with a hue angle ∠h° in the rangeof approximately 15 to 80 degrees), such as light brown, brown (a commoncolor name according to Japanese Industrial Standards (JIS)), darkbrown, chestnut, yellow-brown (yellowish brown), reddish brown(brownish-red), and umber, are likely to change. The present inventorsassume that such a hue change results partly from a difference in lightfastness between dyes in inks.

SUMMARY

An advantage of some aspects of the invention is to provide an ink jetink composition for textile printing that can produce a color with a hueangle ∠h° in the range of 15 to 80 degrees with high colordevelopability in printed textiles without color mixing of differentcolors, that can reduce the temporal hue change (higher light fastness),and that has high ejection reliability (recoverability from long-termclogging or continuous ejection stability). Another advantage of someaspects of the invention is to provide an ink set and a recordingmethod.

The invention has been achieved to solve at least part of the problemsdescribed above and can be implemented in accordance with the followingaspects or application examples.

An ink jet ink composition for textile printing according to an aspectof the invention contains a dye, and 5% to 30% by mass of a cyclic amidethat is liquid at normal temperature and has a normal boiling point inthe range of 190° C. to 260° C., wherein the hue angle ∠h° defined bythe CIELAB color space on a recording medium ranges from 15 to 80degrees.

Such an ink jet ink composition for textile printing can produce a colorwith a hue angle ∠h° in the range of 15 to 80 degrees with high colordevelopability in printed textiles without color mixing of differentcolors, and can reduce the temporal hue change (higher light fastness).High color developability in printed textiles can be achieved by the inkjet ink composition containing 5% to 30% by mass of a cyclic amide witha normal boiling point in the range of 190° C. to 260° C., the cyclicamide enabling a sufficient amount of dye to be dissolved in the ink jetink composition. Furthermore, a color with a hue angle ∠h° in the rangeof 15 to 80 degrees can be produced without color mixing of differentcolors, and the temporal hue change can be reduced (higher lightfastness).

It is preferable that the hue angle ∠h° defined by the CIELAB colorspace on a recording medium range from 20 to 75 degrees.

Such an ink jet ink composition for textile printing can produce a colorin such a range without color mixing of different colors on a textile tobe printed, for example, cotton, silk, wool, or viscose (rayon), and canfurther reduce the temporal hue change (higher light fastness).

It is preferable that the dye have a maximum absorption wavelength inthe range of 350 to 450 nm.

Such an ink jet ink composition for textile printing can produce a colorwith a hue angle ∠h° in the range of 15 to 80 degrees without colormixing of different colors.

It is preferable that the dye be at least one of C.I. Reactive Orange35, C.I. Reactive Orange 12, C.I. Reactive Orange 99, C.I. Acid Brown298, and C.I. Acid Orange 56.

Such an ink jet ink composition for textile printing has still highercolor developability.

It is preferable that the dye content range from 3% to 15% by mass.

Such an ink jet ink composition for textile printing has a sufficientdye content and has still higher color developability.

It is preferable that the ink jet ink composition for textile printinghave a pH in the range of 6 to 10.

Such an ink jet ink composition for textile printing has still highercolor developability.

It is preferable that the ink jet ink composition for textile printingcontain an alkyl polyol with a normal boiling point in the range of 180°C. to 260° C., and the alkyl polyol content range from 10% to 25% bymass.

In such an ink jet ink composition for textile printing, even when a dyecontaining copper is likely to produce foreign matter by drying, thealkyl polyol can increase moisture retention and thereby maintain highrecoverability from long-term clogging and high continuous ejectionstability.

An ink set according to an aspect of the invention contains the ink jetink composition for textile printing.

Such an ink set can produce a color with a hue angle ∠h° in the range of15 to 80 degrees without color mixing of different colors, and canreduce the temporal hue change (higher light fastness) at least in aprinted portion of the color in the hue angle range.

A recording method according to an aspect of the invention includes apretreatment process of applying a pretreatment composition containingat least one of an alkaline agent, an acid, and a hydrotropic agent to atextile, and a printing process of applying the ink jet ink compositionfor textile printing to the textile.

Such a recording method can produce a color with a hue angle ∠h° in therange of 15 to 80 degrees with high color developability in printedtextiles without color mixing of different colors, and can reduce thetemporal hue change (higher light fastness).

BRIEF DESCRIPTION OF THE DRAWING

The invention will be described with reference to the accompanyingdrawing, wherein like numbers reference like elements.

The FIGURE shows the light absorption spectra of C.I. Reactive Orange 35(RO35), C.I. Reactive Orange 12 (RO12), C.I. Reactive Orange 99 (RO99),C.I. Acid Brown 298 (ABr298), and C.I. Acid Orange 56 (AO56) in thevisible light region.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Embodiments of the invention will be described below. These embodimentsare offered by way of illustration only. The invention is not limited tothese embodiments and includes various modified embodiments withoutdeparting from the gist of the invention. Furthermore, all the elementsdescribed below are not necessarily essential for the invention.

1. Ink Jet Ink Composition for Textile Printing

An ink jet ink composition for textile printing according to the presentembodiment (hereinafter also referred to as an ink jet ink compositionfor textile printing or an ink composition) is used by applying apretreatment composition according to the present embodiment describedlater to a textile and subsequently applying the ink jet ink compositionfor textile printing to the textile by an ink jet method. The ink jetink composition for textile printing will be described below.

The ink jet ink composition for textile printing according to thepresent embodiment includes a dye and 5% to 30% by mass of a cyclicamide that is liquid at normal temperature and has a normal boilingpoint in the range of 190° C. to 260° C. The hue angle ∠h° defined bythe CIELAB color space on a recording medium ranges from 15 to 80degrees.

1.1. Dye

The ink jet ink composition for textile printing according to thepresent embodiment contains a dye.

1.1.1. Type of Dye

Specific examples of a dye with which the hue angle ∠h° defined by theCIELAB color space on a recording medium can easily range from 15 to 80degrees in the ink jet ink composition for textile printing include C.I.Reactive Orange 35, C.I. Reactive Orange 12, C.I. Reactive Orange 99,C.I. Acid Brown 298, and C.I. Acid Orange 56.

The chemical structures of C.I. Reactive Orange 35, C.I. Reactive Orange12, C.I. Reactive Orange 99, C.I. Acid Brown 298, and C.I. Acid Orange56 are represented by the following formulae (1), (2), (3), (4), and(5), respectively. A group represented by “—SO₃Na” in each of thechemical formulae herein refers to “—SO₃ ⁻” with a counter ion “Na⁺”.However, the counter ion of the “—SO₃ ⁻” group in each of the formulaemay independently be “H⁺”, “Li⁺”, or “K⁺”.

The dye in the ink jet ink composition for textile printing can providehigh color developability and high temporal stability of hue (lightfastness) irrespective of the type of textile to be printed.

1.1.2. Hue Angle ∠h° Defined by CIELAB Color Space

The ink jet ink composition for textile printing according to thepresent embodiment used in textile printing has a hue angle ∠h° definedby the CIELAB color space on a recording medium in the range of 15 to 80degrees.

The hue angle ∠h° defined by the CIELAB color space is a hue parametercalculated using the following formula from the color coordinates a* andb* of the L*a*b* color space, which is a perceptually almost uniformcolor space recommend by International Commission on Illumination (CIE)in 1976.Hue angle ∠h°=tan⁻¹(b*/a*)

The hue angle ∠h° is also the correlate of hue calculated using theformula (11) in “4.2 Correlates of lightness, chroma, and hue” in “3.6CIELAB 1976 a,b hue-angle” in Japanese Industrial Standards JIS Z8781-4: 2013 “Colorimetry-Part 4: CIE 1976 L*a*b* Color Space” (also see03087 of JIS Z 8113). The “CIE 1976 L*a*b*” can also be called “CIELAB”.

The hue angle ∠h° defined by the CIELAB color space “on a recordingmedium” with respect to an ink jet ink composition for textile printingdefined in the present specification can be determined by measurementaccording to “5. Spectrophotometric colorimetry” in Japanese IndustrialStandards JIS Z 8722: 2009 “Methods of color measurement-Reflecting andtransmitting objects”, for example. The following are measurementconditions.

(1) Prepare an ink jet ink composition for textile printing.

(2) Apply the ink to a textile to be printed.

(3) Allow the ink to react sufficiently by heating, steam, or the like.

(4) Wash the textile.

(5) Perform spectrocolorimetry.

The hue angle ∠h° is calculated from the measurement results as the hueangle ∠h° defined by the CIELAB color space “on a recording medium” withrespect to an ink jet ink composition for textile printing. Therecording material is preferably white.

The ink jet ink composition for textile printing can be adjusted suchthat the hue angle ∠h° defined by the CIELAB color space on a recordingmedium ranges from 15 to 80 degrees by changing the dye or by mixingwith a dye with a different hue angle. More specifically, the hue angle∠h° defined by the CIELAB color space on a recording medium can beadjusted by changing the number of aromatic rings or substituents or thetype of aromatic ring or substituent to modify a conjugated system in aspecific dye, by changing the central metal, if present, in a specificdye, or by mixing a specific dye with another dye.

Among these methods, when the hue angle is adjusted by mixing the inkjet ink composition for textile printing with another dye, the amount ofthe other dye is preferably smaller, for example, 1% or less by mass,preferably 0.5% or less by mass, more preferably 0.3% or less by mass,still more preferably 0.1% or less by mass, particularly preferably0.05% or less by mass, of the ink jet ink composition for textileprinting. Thus, even when each dye fades over time, the change in hueangle in a printed portion can be reduced. When another dye is mixed,the other dye preferably has a hue angle closer to the hue angle of theoriginal dye. In this case, the amount of the other dye can beincreased, for example, to 2% or less by mass, preferably 1% or less bymass, more preferably 0.5% or less by mass, still more preferably 0.3%or less by mass, particularly preferably 0.1% or less by mass, of theink jet ink composition for textile printing.

Although multiple types of dyes may be used, a single type of dye ispreferably used in order to reduce the change in hue angle in a printedportion. Thus, the ink jet ink composition for textile printingaccording to the present embodiment preferably contains a single dye. Inthis case, another dye may be contained as an impurity. Morespecifically, the total amount of dyes contained as impurities is 1% orless by mass, preferably 0.1% or less by mass, more preferably 0.01% orless by mass, still more preferably 0.001% or less by mass, particularlypreferably 0.0001% or less by mass, of the dye(s) in the ink jet inkcomposition for textile printing. This enables textile printingsubstantially only with a single dye and is further desirable because aprinted portion has a negligible change in hue angle even when the dyefades over time.

The total amount of dye(s) in the ink jet ink composition for textileprinting according to the present embodiment ranges from 2% to 30% bymass, preferably 3% to 15% by mass, more preferably 4% to 10% by mass,of the total mass of the ink jet ink composition for textile printing.

The dye in the ink jet ink composition for textile printing according tothe present embodiment is more preferably at least one selected fromC.I. Reactive Orange 35, C.I. Reactive Orange 12, C.I. Reactive Orange99, C.I. Acid Brown 298, and C.I. Acid Orange 56. Among these, C.I.Reactive Orange 35 and C.I. Acid Brown 298 are particularly preferred.The selection of such a dye can produce a color with a hue angle ∠h° inthe range of 15 to 80 degrees with high color developability in printedtextiles without color mixing of different colors, and can reduce thetemporal hue change (higher light fastness). Containing at least thesedyes can provide high color developability in printed textiles. Due toits improved light fastness, C.I. Reactive Orange 35 or C.I. Acid Brown298 can be used to produce a color with a hue angle ∠h° in the range of20 to 75 degrees without color mixing of different colors and to greatlyreduce the temporal hue change (higher light fastness).

Furthermore, C.I. Reactive Orange 35 or C.I. Acid Brown 298 can be usedalone to produce a color with a hue angle ∠h° in the range of 20 to 75degrees without color mixing of different colors. The hue angle ∠h°defined by the CIELAB color space on a recording medium may range from20 to 75 degrees.

Such an ink jet ink composition for textile printing can produce a colorin such a range without color mixing of different colors on a textile tobe printed, for example, cotton, silk, wool, viscose (rayon), or apolyamide (PA) elastomer, and can further reduce the temporal hue change(higher light fastness). This can provide better light fastness (asmaller temporal hue change) than a composite ink containing multipletypes of dyes or a known technique of producing a brown hue by combininginks of different hues (for example, producing a brown color with an inkset of four YMCK colors).

Although the dye in the ink jet ink composition for textile printingaccording to the present embodiment is described above, the dye is morepreferably a dye with a maximum absorption wavelength in the range of350 to 450 nm.

The maximum absorption wavelength can be measured by dissolving a dye ina solvent (water, an organic solvent, or a liquid mixture thereof) at anappropriate concentration to prepare a solution and measuring the lightabsorption spectrum of the solution in the visible light region. Even inthe case where the light absorption spectrum in the visible light regionhas a plurality of peaks, the maximum absorption wavelength refers tothe wavelength of the maximum absorbance. The maximum absorptionwavelength of a dye can be measured even in an ink composition in whichthe dye is dissolved. Depending on the concentration of the dye, the inkcomposition can be diluted 500- to 2000-fold with water to prepare adiluted solution for the measurement.

A dye with a maximum absorption wavelength in the range of 350 to 450 nmtypically produces a color with a hue angle ∠h° in the range of 15 to 80degrees. C.I. Reactive Orange 35, C.I. Reactive Orange 12, C.I. ReactiveOrange 99, C.I. Acid Brown 298, and C.I. Acid Orange 56 have a maximumabsorption wavelength in the range of 350 to 450 nm. C.I. ReactiveOrange 35, C.I. Reactive Orange 12, C.I. Reactive Orange 99, C.I. AcidBrown 298, and C.I. Acid Orange 56 have the following maximum absorptionwavelengths.

C.I. Reactive Orange 35 maximum absorption wavelength: 414 nm

C.I. Reactive Orange 12 maximum absorption wavelength: 420 nm

C.I. Reactive Orange 99 maximum absorption wavelength: 420 nm

C.I. Acid Brown 298 maximum absorption wavelength: 362 nm

C.I. Acid Orange 56 maximum absorption wavelength: 414 nm

The FIGURE shows the light absorption spectra of C.I. Reactive Orange35, C.I. Reactive Orange 12, C.I. Reactive Orange 99, C.I. Acid Brown298, and C.I. Acid Orange 56. The spectra in the FIGURE were measured inan aqueous solution containing 10 ppm of dye with a double-beamspectrophotometer U-3300 (trade name, manufactured by HitachiHigh-Technologies Corporation) using a quartz cell with an optical pathlength of 10 mm. The light absorption spectrum of a dye may be measuredby any other method.

1.2. Cyclic Amide

The ink jet ink composition for textile printing according to thepresent embodiment contains a cyclic amide that is liquid at normaltemperature (25° C. or, more preferably, 23° C.) and that has a normalboiling point (at 1 atm pressure) in the range of 190° C. to 260° C.Such a cyclic amide has the functions of facilitating the dissolution ofsuch a dye as described above and suppressing solidification or dryingof the ink jet ink composition for textile printing. With a normalboiling point in the range of 190° C. to 260° C., the cyclic amide hassufficiently low volatility and high moisture-holding capacity, therebymore effectively suppressing solidification or drying of the ink jet inkcomposition for textile printing.

The cyclic amide may be a compound with a ring structure including anamide group, for example, a compound represented by the followingformula (6).

In the formula (6), R¹ denotes hydrogen or an alkyl group with 1 to 4carbon atoms, and n denotes an integer in the range of 1 to 4. The alkylgroup may be linear or branched.

The compound represented by the formula (6) may be a γ-lactam, β-lactam,or δ-lactam, such as 2-pyrrolidone [245° C.], 1-methyl-2-pyrrolidone[204° C.] (N-methyl-2-pyrrolidone), 1-ethyl-2-pyrrolidone [212° C.](N-ethyl-2-pyrrolidone), N-vinyl-2-pyrrolidone [193° C.],1-propyl-2-pyrrolidone, or 1-butyl-2-pyrrolidone. The FIGURES inparentheses indicate the normal boiling points. These cyclic amides maybe used alone or in combination.

Among cyclic amide compounds, compounds that are liquid at normaltemperature include 2-pyrrolidone (25° C.), 1-methyl-2-pyrrolidone (−24°C.), 1-ethyl-2-pyrrolidone (−77° C.), and N-vinyl-2-pyrrolidone (14° C.)The FIGURES in parentheses indicate the melting points. Although2-pyrrolidone has a high melting point of 25° C. and may be solid atnormal temperature (for example, at room temperature, 23° C., 25° C.,etc.) at the time of purchase, after melting, for example, with warmwater at approximately 40° C., 2-pyrrolidone can maintain the liquidstate at normal temperature. The present inventors assume that thisphenomenon results from the supercooled state or freezing pointdepression due to water or the like. In the invention, such a state isalso considered to be liquid at normal temperature.

The total cyclic amide content ranges from 1% to 30% by mass, preferably5% to 30% by mass, more preferably 5% to 25% by mass, still morepreferably 7% to 15% by mass, of the total mass of the ink composition.

A total cyclic amide content in this range results in sufficientdissolution of a dye and an increase in the amount (concentration) of adye to be used. More specifically, among various dyes, some dyes (forexample, C.I. Reactive Orange 35, C.I. Reactive Orange 12, C.I. ReactiveOrange 99, C.I. Acid Brown 298, and C.I. Acid Orange 56, particularlyC.I. Reactive Orange 35 and C.I. Acid Brown 298) do not necessarily havehigh solubility in the ink jet ink composition for textile printing, andtherefore it is relatively difficult to increase the concentration ofthe dyes to improve color development. However, the use of the cyclicamide can increase the amount of dye and further improve the colordevelopability of a printed textile.

1.3. Other Components

The ink jet ink composition for textile printing according to thepresent embodiment can contain the following components as well as thecomponents described above.

1.3.1. Alkyl Polyol

The ink jet ink composition for textile printing according to thepresent embodiment may contain an alkyl polyol with a normal boilingpoint in the range of 180° C. to 260° C. Such an alkyl polyol canfurther increase the moisture retention of the ink jet ink compositionfor textile printing, improve ejection stability in the ink jet method,and effectively reduce water evaporation from a recording head when therecording head is unused for extended periods. This ensures highrecoverability from long-term clogging and high continuous ejectionstability even when a dye used is likely to cause nozzle clogging.

Specific examples of the alkyl polyol with a normal boiling point in therange of 180° C. to 260° C. include, 1,2-butanediol [194° C.],1,2-pentanediol [210° C.], 1,2-hexanediol [224° C.], 1,2-heptanediol[227° C.], 1,3-propanediol [210° C.], 1,3-butanediol [230° C.],1,4-butanediol [230° C.], 1,5-pentanediol [242° C.], 1,6-hexanediol[250° C.], 2-ethyl-2-methyl-1,3-propanediol [226° C.],2-methyl-2-propyl-1,3-propanediol [230° C.], 2-methyl-1,3-propanediol[214° C.], 2,2-dimethyl-1,3-propanediol [210° C.],3-methyl-1,3-butanediol [203° C.], 2-ethyl-1,3-hexanediol [244° C.],3-methyl-1,5-pentanediol [250° C.], 2-methylpentane-2,4-diol [197° C.],diethylene glycol [245° C.], and dipropylene glycol [232° C.] TheFIGURES in parentheses indicate the normal boiling points. These alkylpolyols may be used alone or in combination.

The effective amount of the alkyl polyol with a normal boiling point inthe range of 180° C. to 260° C. is 5% or more by mass, preferably 5% to30% by mass, more preferably 8% to 27% by mass, still more preferably10% to 25% by mass, of the total mass of the ink jet ink composition fortextile printing.

The ink jet ink composition for textile printing according to thepresent embodiment contains no alkyl polyol with a normal boiling pointof 260° C. or more. This is because alkyl polyols with a normal boilingpoint of 260° C. or more are likely to reduce the dyeing affinity ofdyes and the color reproducibility and color developability of images.Specific examples of alkyl polyols with a normal boiling point of 260°C. or more include triethylene glycol [287° C.] and glycerin [290° C.]

The phrase “contains no A”, as used herein, refers not only tocontaining no A but also to no intentional addition of A in theproduction of a composition, and includes inevitable contamination orgeneration of a minute amount of A during the production or storage ofthe composition. Specific examples of “contains no . . . ” include notcontaining 1.0% or more by mass, preferably 0.5% or more by mass, morepreferably 0.1% or more by mass, still more preferably 0.05% or more bymass, particularly preferably 0.01% or more by mass.

1.3.2. Surfactant

The ink jet ink composition for textile printing according to thepresent embodiment may contain a surfactant. The surfactant can be usedto reduce the surface tension of the ink jet ink composition for textileprinting and to adjust or improve wettability to a recording medium(penetrability to a textile). The surfactant may be a nonionicsurfactant, an anionic surfactant, a cationic surfactant, an amphotericsurfactant, or a combination thereof. Among such surfactants, acetyleneglycol surfactants, silicone surfactants, and fluorinated surfactantsare preferred.

Examples of the acetylene glycol surfactants include, but are notlimited to, Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA,104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 504, 61, DF37, CT111,CT121, CT131, CT136, TG, GA, and DF110D (trade names, manufactured byAir Products and Chemicals. Inc.), Olfin B, Y, P, A, STG, SPC, E1004,E1010, PD-001, PD-002W, PD-003, PD-004, PD-005, EXP.4001, EXP.4036,EXP.4051, AF-103, AF-104, AK-02, SK-14, and AE-3 (trade names,manufactured by Nissin Chemical Industry Co., Ltd.), and Acetylenol E00,E00P, E40, and E100 (trade names, manufactured by Kawaken Fine ChemicalsCo., Ltd.).

Preferred examples of the silicone surfactants include, but are notlimited to, polysiloxane compounds. Examples of the polysiloxanecompounds include, but are not limited to, polyether-modifiedorganosiloxanes. Examples of the commercial products of thepolyether-modified organosiloxanes include BYK-306, BYK-307, BYK-333,BYK-341, BYK-345, BYK-346, and BYK-348 (trade names, manufactured byBYK), and KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945,KF-640, KF-642, KF-643, KF-6020, X-22-4515, KF-6011, KF-6012, KF-6015,and KF-6017 (trade names, manufactured by Shin-Etsu Chemical Co., Ltd.).

Preferred examples of the fluorinated surfactants includefluorine-modified polymers, for example, BYK-340 (manufactured by BYKJapan KK).

The total amount of surfactant(s), if present, in the ink jet inkcomposition for textile printing ranges from 0.01% to 3% by mass,preferably 0.05% to 2% by mass, more preferably 0.1% to 1.5% by mass,particularly preferably 0.2% to 1% by mass, of the ink jet inkcomposition for textile printing.

A surfactant in the ink jet ink composition for textile printing tendsto increase stability in the ejection of ink from a head. The use of anappropriate amount of surfactant can improve penetrability to a textileand increase the contact area with a pretreatment composition.

1.3.3. pH-Adjusting Agent

The ink composition according to the present embodiment may contain apH-adjusting agent to adjust pH. The pH-adjusting agent may be, but isnot limited to, a combination of an acid, a base, a weak acid, and aweak base. Examples of an acid and a base used in such a combinationinclude inorganic acids, such as sulfuric acid, hydrochloric acid, andnitric acid, inorganic bases, such as lithium hydroxide, sodiumhydroxide, potassium hydroxide, potassium dihydrogen phosphate, disodiumhydrogen phosphate, potassium carbonate, sodium carbonate, sodiumhydrogen carbonate, and ammonia, organic bases, such as triethanolamine,diethanolamine, monoethanolamine, tripropanolamine, triisopropanolamine,diisopropanolamine, and trishydroxymethylaminomethane (THAM), organicacids, such as adipic acid, citric acid, succinic acid, and lactic acid.Good's buffers, such as N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonicacid (BES), 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES),morpholinoethanesulfonic acid (MES), carbamoylmethyliminobisacetic acid(ADA), piperazine-1,4-bis(2-ethanesulfonic acid) (PIPES),N-(2-acetamide)-2-aminoethanesulfonic acid (ACES), cholamine chloride,N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid (TES),acetamidoglycine, tricine, glycinamide, and bicine, phosphate buffers,citric acid buffers, and Tris buffers may also be used. Among these, atertiary amine, such as triethanolamine or triisopropanolamine, and/oran organic acid with a carboxy group, such as adipic acid, citric acid,succinic acid, or lactic acid, is preferably partly or entirely used asthe pH-adjusting agent in order to produce more stable pH-bufferingeffects.

1.3.4. Water

The ink jet ink composition for textile printing according to thepresent embodiment may contain water. Examples of the water include purewaters, such as ion-exchanged water, ultrafiltered water, reverseosmosis water, and distilled water, and waters from which ionicimpurities are removed as much as possible, such as ultrapure water. Theuse of water sterilized by ultraviolet irradiation or by the addition ofhydrogen peroxide can reduce the growth of bacteria and fungi duringlong-term storage of the ink jet ink composition for textile printing.

The water content is 30% or more by mass, preferably 40% or more bymass, more preferably 45% or more by mass, still more preferably 50% ormore by mass, of the total amount of the ink jet ink composition fortextile printing. The term “water” in the ink jet ink composition fortextile printing includes a resin particle dispersion liquid used as araw material and water added, for example. A water content of 30% ormore by mass can result in the ink jet ink composition for textileprinting with a relatively low viscosity. The upper limit of the watercontent is preferably 90% or less by mass, more preferably 85% or lessby mass, still more preferably 80% or less by mass, of the total amountof the ink jet ink composition for textile printing.

1.3.5. Organic Solvent

The ink jet ink composition for textile printing according to thepresent embodiment may contain a cyclic amide with a normal boilingpoint of less than 190° C. or more than 260° C., a nitrogen-containingheterocyclic compound, and/or a water-soluble organic solvent. Thecyclic amide with a normal boiling point of less than 190° C. or morethan 260° C. may be a lactam, such as ε-caprolactam [136° C.]. Thewater-soluble organic solvent may be a lactone, such as γ-butyrolactone[204° C.], or a betaine compound. The ink jet ink composition fortextile printing according to the present embodiment may contain aglycol ether, with which the wettability and penetration speed of thecomposition may be controlled. This may improve the color developabilityof images.

The glycol ether with a normal boiling point in the range of 190° C. to260° C. is preferably a glycol monoalkyl ether selected from ethyleneglycol, diethylene glycol, triethylene glycol, poly(ethylene glycol),propylene glycol, dipropylene glycol, tripropylene glycol,poly(propylene glycol), and polyoxyethylene polyoxypropylene glycol.More preferably, the glycol ether with a normal boiling point in therange of 190° C. to 260° C. may be methyltriglycol (triethylene glycolmonomethyl ether), butyltriglycol (triethylene glycol monobutyl ether),butyl diglycol (diethylene glycol monobutyl ether), or dipropyleneglycol monopropyl ether, typically diethylene glycol monobutyl ether[230° C.]. The FIGURES in parentheses indicate the normal boilingpoints.

Such organic solvents may be used in combination. In order to controlthe viscosity of the ink jet ink composition for textile printing and toprevent clogging by the moisturizing effects, the total amount oforganic solvent(s) ranges from 0.2% to 30% by mass, preferably 0.4% to20% by mass, more preferably 0.5% to 15% by mass, still more preferably0.7% to 10% by mass, of the total amount of the ink jet ink compositionfor textile printing.

1.3.6. Urea

A urea may be used as a humectant in the ink jet ink composition fortextile printing or as a dyeing aid for improving the dyeing affinity ofa dye. Specific examples of the urea include urea, ethyleneurea,tetramethylurea, thiourea, and 1,3-dimethyl-2-imidazolidinone. Theamount of urea, if present, ranges from 1% to 10% by mass of the totalmass of the ink composition.

1.3.7. Saccharide

A saccharide may be used to prevent solidification or drying of the inkjet ink composition for textile printing. Specific examples of thesaccharide include, glucose, mannose, fructose, ribose, xylose,arabinose, galactose, aldonic acid, glucitol (sorbitol), maltose,cellobiose, lactose, sucrose, trehalose, and maltotriose.

1.3.8. Chelating Agent

A chelating agent may be used to remove unnecessary ions from the inkjet ink composition for textile printing. Examples of the chelatingagent include ethylenediaminetetraacetic acid and salts thereof(disodium dihydrogen ethylenediaminetetraacetate, or ethylenediaminenitrilotriacetate, hexametaphosphate, pyrophosphate, or metaphosphate,etc.).

1.3.9. Preservative, Fungicide

The ink jet ink composition for textile printing may contain apreservative and/or a fungicide. Examples of the preservative andfungicide include sodium benzoate, pentachlorophenol sodium,2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate,1,2-benzisothiazolin-3-one (Proxel CRL, Proxel BDN, Proxel GXL, ProxelXL.2, Proxel TN, and Proxel LV, manufactured by Zeneca), and4-chloro-3-methylphenol (Preventol CMK manufactured by Bayer AG, etc.).

1.3.10. Others

In addition to these components, additive agents generally used in inkcompositions for ink jet, such as an anticorrosive, an antioxidant, anultraviolet absorber, an oxygen absorbent, and/or a dissolution aid maybe used. 1.4. pH of Ink Jet Ink Composition for Textile Printing

The ink jet ink composition for textile printing according to thepresent embodiment preferably has a pH in the range of 5.8 to 10.5, morepreferably 6.0 to 10.0, still more preferably 6.0 to 9.5, still morepreferably 7.0 to 8.5. In the ink jet ink composition for textileprinting with a pH in this range, a dye in the ink composition hasimproved storage stability, and the resulting images are less likely tohave color developability and hue changes. Thus, predetermined designcolors can be well reproduced.

The pH of the ink jet ink composition for textile printing can beadjusted to be in the range, for example, by changing the liquidity of adye, the type of counter ion of an ionic dye and a balance thereof, orthe type or amount of pH-adjusting agent.

1.5. Production and Physical Properties of Ink Composition

The ink composition according to the present embodiment is produced bymixing the components in any order and, if necessary, filtering themixture to remove impurities. The components are preferably sequentiallycharged and mixed in a container equipped with an agitator, such as amechanical stirrer or a magnetic stirrer.

The ink composition according to the present embodiment preferably has asurface tension in the range of to 40 mN/m, more preferably 22 to 35mN/m, from the perspective of the balance between printing quality andreliability as the ink jet ink for textile printing. From the sameperspective, the ink composition preferably has a viscosity in the rangeof 1.5 to 10 mPa·s, more preferably 2 to 8 mPa·s, at 20° C. The surfacetension and viscosity can be adjusted to be in these ranges by changingthe type of water-soluble solvent and the type of surfactant and bychanging the amount of water-soluble solvent, surfactant, and water.

1.6. Operational Advantages

The ink jet ink composition for textile printing according to thepresent embodiment can produce a color with a hue angle ∠h° in the rangeof 15 to 80 degrees with high color developability in printed textileswithout color mixing of different colors, and can reduce the temporalhue change (higher light fastness). High color developability in printedtextiles can be achieved by the ink jet ink composition containing 5% to30% by mass of a cyclic amide with a normal boiling point in the rangeof 190° C. to 260° C., the cyclic amide enabling a sufficient amount ofdye to be dissolved in the ink jet ink composition. Furthermore, a colorwith a hue angle ∠h° in the range of 15 to 80 degrees can be producedwithout color mixing of different colors, and the temporal hue changecan be reduced (higher light fastness).

2. Ink Set

The ink jet ink composition for textile printing according to thepresent embodiment, an ink jet ink composition for textile printingcontaining a dye of another color, and a pretreatment compositiondescribed later can be combined in any number of compositions and in anynumber of colors to compose an ink set.

The ink set according to the present embodiment can produce a color witha hue angle ∠h° in the range of 15 to degrees with high colordevelopability in printed textiles without color mixing of differentcolors, and can reduce the temporal hue change (higher light fastness).The use of C.I. Reactive Orange 35 or C.I. Acid Brown 298 can produce acolor with a hue angle ∠h° in the range of 20 to degrees, preferably 25to 70 degrees, without color mixing of different colors and can greatlyreduce the temporal hue change (higher light fastness).

The ink jet ink composition for textile printing according to thepresent embodiment, together with a pretreatment composition describedlater, can compose an ink set. The pretreatment composition can furtherimprove textile printing.

The ink set according to the present embodiment can produce a color witha hue angle ∠h° in the range of 15 to 80 degrees without color mixing ofdifferent colors, and can reduce the temporal hue change (higher lightfastness) at least in a printed portion of the color in the hue anglerange.

3. Recording Method

Printing Method

A recording method according to the present embodiment includes aprocess of applying the ink jet ink composition for textile printing toa textile (hereinafter also referred to as a “printing process”). Aprocess that is or can be included in the recording method according tothe present embodiment will be described below.

3.1. Recording Medium

The ink jet ink composition for textile printing according to thepresent embodiment is applied to a recording medium. The recordingmedium may be, but is not limited to, a textile. The material for thetextile may be, but is not limited to, natural fiber, such as cotton,hemp, wool, or silk, synthetic fiber, such as polypropylene, polyester,acetate, triacetate, polyamide, or polyurethane, biodegradable fiber,such as poly(lactic acid), or a mixed fiber thereof. The textile may bea fabric, knit fabric, or nonwoven fabric of the fiber. Among these, thetextile for use in the present embodiment is more preferably formed offiber containing cellulose, such as cotton or hemp. The use of such atextile can improve the dyeing affinity of the ink jet ink compositionfor textile printing.

The mass per unit area of a textile used in the present embodimentranges from 1.0 to 10.0 oz (ounce), preferably 2.0 to 9.0 oz, morepreferably 3.0 to 8.0 oz, still more preferably 4.0 to 7.0 oz.

3.2. Pretreatment Process

The recording method according to the present embodiment may include apretreatment process of applying a pretreatment composition containingat least one of an alkaline agent, an acid, and a hydrotropic agent to atextile. This further improves the dyeing affinity of a dye.

The pretreatment composition can be applied to a textile, for example,by immersing the textile in the pretreatment composition, by applyingthe pretreatment composition to the textile with a roll coater, or byejecting the pretreatment composition (for example, an ink jet method ora spray method).

Pretreatment Composition

The pretreatment composition contains at least one of an alkaline agent,an acid, and a hydrotropic agent. The amounts of these components in thepretreatment composition depend on the type of textile and are notparticularly limited.

When a reactive dye is used, an alkaline agent is preferably used tofurther improve the dyeing affinity of the reactive dye. Specificexamples of the alkaline agent include, sodium carbonate, sodiumhydrogen carbonate, sodium hydroxide, trisodium phosphate, and sodiumacetate.

When an acidic dye is used, an acid is preferably used to furtherimprove the dyeing affinity of the dye. Specific examples of the acidinclude organic acids, such as organic carboxylic acids with a carboxygroup in the molecule and organic sulfonic acids with a sulfo group inthe molecule, and ammonium salts of strong acids. Among these, ammoniumsulfate is particularly preferred.

A hydrotropic agent is preferably used to improve the colordevelopability of images recorded. The hydrotropic agent may be a ureathat is exemplified in the section of the ink jet ink composition fortextile printing.

The pretreatment composition in the present embodiment may containwater. The water is described above with respect to the ink jet inkcomposition for textile printing. The water content is 30% or more bymass, preferably 40% or more by mass, more preferably 45% or more bymass, still more preferably 50% or more by mass, of the total amount ofthe pretreatment composition.

The pretreatment composition in the present embodiment may contain awater-soluble organic solvent. The water-soluble organic solvent mayimprove the wettability of the pretreatment composition to a recordingmedium. The water-soluble organic solvent may be at least one of esters,alkylene glycol ethers, cyclic esters, and alkoxyalkylamides. Thewater-soluble organic solvent may also be a nitrogen-containingcompound, a saccharide, or an amine. The pretreatment composition maycontain a water-soluble organic solvent for use in the ink jet inkcomposition for textile printing.

The pretreatment composition may contain two or more water-solubleorganic solvents. The total amount of water-soluble organic solvent(s),if present, in the pretreatment composition ranges from 0.1% to 20% bymass, preferably 0.3% to 15% by mass, more preferably 0.5% to 10% bymass, still more preferably 1% to 7% by mass, of the pretreatmentcomposition.

The pretreatment composition may contain a sizing agent. Examples of thesizing agent include starches, such as maize and wheat, celluloses, suchas carboxymethylcellulose and hydroxymethylcellulose, polysaccharides,such as sodium alginate, gum arabic, locust bean gum, gum tragacanth,guar gum, and tamarind seed, proteins, such as gelatin and casein,natural water-soluble polymers, such as tannin and lignin, and syntheticwater-soluble polymers, such as poly(vinyl alcohol) compounds,poly(ethylene oxide) compounds, acrylic acid compounds, and maleicanhydride compounds.

The pretreatment composition in the present embodiment may contain asurfactant. The surfactant is described above with respect to the inkjet ink composition for textile printing. The total amount ofsurfactant(s), if present, in the pretreatment composition preferablyranges from 0.01% to 3% by mass, more preferably 0.05% to 2% by mass,still more preferably 0.1% to 1% by mass, particularly preferably 0.2%to 0.5% by mass, of the pretreatment composition. A surfactant in thepretreatment composition can control the penetrability and wettabilityof ink applied to a pretreated textile and can thereby improve the colordevelopability or suppress the blurring of a printed textile.

The pretreatment composition in the present embodiment may containcomponents commonly used in pretreatment compositions for textileprinting, such as water, a reduction inhibitor, a preservative, afungicide, a chelating agent, a pH-adjusting agent, a surfactant, aviscosity modifier, an antioxidant, and a fungicide.

The pretreatment composition may be applied to a textile by an ink jetmethod and, in this case, preferably has a viscosity in the range of 1.5to 15 mPa·s, more preferably 1.5 to 5 mPa·s, still more preferably 1.5to 3.6 mPa·s, at 20° C.

The pretreatment composition may be applied by a method other than theink jet method. Such a method may be a noncontact method or a contactmethod or a combination thereof, such as a method for applying apretreatment composition to a textile with a spray, a method forimmersing a textile in a pretreatment composition, or a method forapplying a treatment liquid to a textile with a brush.

A pretreatment composition to be applied to a textile by a method otherthan the ink jet method may have a higher viscosity than that to beapplied by the ink jet method, for example, preferably a viscosity inthe range of 1.5 to 100 mPa·s, more preferably 1.5 to 50 mPa·s, stillmore preferably 1.5 to 20 mPa·s, at 20° C. The viscosity can be measuredwith a rheometer MCR-300 (manufactured by Physica) at 20° C. byincreasing the shear rate from 10 to 1000 and reading the viscosity at ashear rate of 200.

3.3. Printing Process

The recording method according to the present embodiment includes aprinting process of applying the ink jet ink composition for textileprinting to a textile. More specifically, ink droplets ejected by an inkjet recording method are deposited on a textile to form an image on thetextile. The ink jet recording method may be any method, for example, acharge deflection method, a continuous method, or an on-demand method (apiezoelectric method or a Bubble Jet (registered trademark) method).Among these ink jet recording methods, a method with a piezoelectric inkjet recording apparatus is particularly preferred.

3.4. Heat-Treatment Process

The recording method according to the present embodiment may include aheat-treatment process of heat-treating a textile to which the inkcomposition is applied. The heat-treatment process improves the dyeingof fiber. The heat-treatment process may be a known process, forexample, a high-temperature steaming process (HT process), ahigh-pressure steaming process (HP process), or a thermosol process.

The temperature of the heat-treatment process preferably ranges from 90°C. to 110° C. in order to reduce damage to a textile.

3.5. Cleaning Process

The recording method according to the present embodiment may include acleaning process of cleaning a printed textile. The cleaning process ispreferably performed after the heat-treatment process to effectivelyremove dye that is not deposited on the fiber. The cleaning process maybe performed with water and may involve soaping treatment, if necessary.

3.6. Another Process

The recording method according to the present embodiment may include apretreatment composition drying process of drying the pretreatmentcomposition on a textile after the pretreatment process and before theprinting process. Although the pretreatment composition may be dried bynatural drying, drying by heating is preferred due to high drying speed.Heating in the pretreatment composition drying process may be performedby any heating method, for example, a heat press method, anormal-pressure steam method, a high-pressure steam method, or aThermofix method. The heat source may be, but is not limited to,infrared light (lamp).

3.7. Operational Advantages

In the recording method according to the present embodiment, the use ofthe ink jet ink composition for textile printing in the printing processcan produce a color with a hue angle ∠h° in the range of 15 to 80degrees with high color developability in printed textiles without colormixing of different colors, can reduce the temporal hue change (higherlight fastness), and can improve ejection reliability (recoverabilityfrom long-term clogging or continuous ejection stability).

4. Examples and Comparative Examples

Although the invention will be further described with examples, theinvention is not limited to these examples.

4.1. Preparation of Ink Jet Ink Composition for Textile Printing

The components of each composition listed in Table 1 were mixed in acontainer with a magnetic stirrer for 2 hours and were then filteredthrough a membrane filter with a pore size of 5 μm to produce inkcompositions of the examples and comparative examples. The values inTable 1 are expressed in % by mass. Ion-exchanged water was added suchthat the total mass of each ink composition was 100% by mass.

TABLE 1 Example (mass %) 1 2 3 4 5 6 7 8 9 10 11 12 13 Reactive dye C.I.Reactive 7.5 — — 6.5 7.5 3 15 7.5 7.5 7.5 2 18 7.5 Orange 35 C.I.Reactive — 7.5 — 0.5 — — — — — — — — — Orange 12 C.I. Reactive — — 7.50.5 — — — — — — — — — Orange 99 C.I. Reactive — — — — — — — — — — — — —Yellow 2 C.I. Reactive — — — — — — — — — — — — — Red 31 Acidic dye C.I.Acid — — — — — — — — — — — — — Brown 298 C.I. Acid — — — — — — — — — — —— — Orange 56 C.I. Acid — — — — — — — — — — — — — Red 289 C.I. Acid — —— — — — — — — — — — — Yellow 79 Nitrogen- N-ethyl-2- — — — — 7 — — — — —— — — containing pyrrolidone heterocyclic (bp = 212° C.) compound2-pyrrolidone 7 7 7 7 — 6 15 7 7 7 7 25 7 (bp = 245° C.) Alkyl polyolPropylene glycol 7 7 7 7 7 7 7 7 7 7 7 7 7 (bp = 188° C.) 1,2-hexanediol3 3 3 3 3 3 3 3 3 3 3 3 3 (bp = 223° C.) Diethylene glycol 8 8 8 8 8 8 88 8 8 8 8 8 (bp = 245° C.) Triethylene glycol — — — — — — — — — — — — —(bp = 287° C.) pH-adjusting Triethanolamine 0.5 0.4 0.6 0.5 0.5 0.5 0.5— — — 0.5 0.3 0.5 agent BES — — — — — — — 2 — — — — — Tripropanolamine —— — — — — — — 1.8 — — — — Sodium — — — — — — — — — 2 — — — dihydrogenphosphate Disodium — — — — — — — — — 2 — — — hydrogen phosphate Adipicacid — — — — — — — — 0.3 — — — — NaOH — — — — — — — 0.5 — — — — 1.5Other Olfin PD-002W 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1additives Urea 5 5 5 5 5 5 5 5 5 5 5 5 5 Proxel XL2 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Water Ion-exchanged Remainder RemainderRemainder Remainder Remainder Remainder Remainder Remainder RemainderRemainder Remainder Remainder Remainder water Total 100 100 100 100 100100 100 100 100 100 100 100 100 Example Comparative example (mass %) 1415 16 17 18 19 20 1 2 3 4 5 Reactive dye C.I. Reactive 7.5 7.5 7.5 7.5 —— — — — 7.5 7.5 — Orange 35 C.I. Reactive — — — — — — — — — — — — Orange12 C.I. Reactive — — — — — — — — — — — — Orange 99 C.I. Reactive — — — —— — — 7.5 6 — — — Yellow 2 C.I. Reactive — — — — — — — — 1.5 — — — Red31 Acidic dye C.I. Acid — — — — 3 — 2 — — — — — Brown 298 C.I. Acid — —— — — 4 — — — — — — Orange 56 C.I. Acid — — — — — — — — — — — 2 Red 289C.I. Acid — — — — — — — — — — — 1 Yellow 79 Nitrogen- N-ethyl-2- — — — —— — — — — — — — containing pyrrolidone heterocyclic (bp = 212° C.)compound 2-pyrrolidone 7 7 7 7 7 7 7 7 7 4 31 31 (bp = 245° C.) Alkylpolyol Propylene glycol 7 3 12 7 3 12 7 7 7 7 7 7 (bp = 188° C.)1,2-hexanediol 3 2 5 3 2 5 3 3 3 3 3 3 (bp = 223° C.) Diethylene glycol8 4 13 — 4 13 — 8 8 8 8 8 (bp = 245° C.) Triethylene glycol — — — 8 — —8 — — — — — (bp = 287° C.) pH-adjusting Triethanolamine — 0.5 0.5 0.50.5 0.5 0.5 0.3 0.7 0.5 0.5 0.5 agent BES 2 — — — — — — — — — — —Tripropanolamine — — — — — — — — — — — — Sodium — — — — — — — — — — — —dihydrogen phosphate Disodium — — — — — — — — — — — — hydrogen phosphateAdipic acid — — — — — — — — — — — — NaOH 0.11 — — — — — — — — — — —Other Olfin PD-002W 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1additives Urea 5 5 5 5 5 5 5 5 5 5 5 5 Proxel XL2 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 0.1 0.1 Water Ion-exchanged Remainder RemainderRemainder Remainder Remainder Remainder Remainder Remainder RemainderRemainder Remainder Remainder water Total 100 100 100 100 100 100 100100 100 100 100 100

The components not described by their compound names in Table 1 were asfollows:

C.I. Reactive Orange 35 maximum absorption wavelength: 414 nm

C.I. Reactive Orange 12 maximum absorption wavelength: 420 nm

C.I. Reactive Orange 99 maximum absorption wavelength: 420 nm

C.I. Reactive Yellow 2 maximum absorption wavelength: 404 nm

C.I. Reactive Red 31 maximum absorption wavelength: 546 nm

C.I. Acid Brown 298 maximum absorption wavelength: 362 nm

C.I. Acid Orange 56 maximum absorption wavelength: 414 nm

C.I. Acid Red 289 maximum absorption wavelength: 527 nm

C.I. Acid Yellow 79 maximum absorption wavelength: 402 nm

BES (N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid: reagent)

Olfin PD-002W (trade name, manufactured by Nissin Chemical Industry Co.,Ltd., acetylene glycol surfactant)

Proxel XL2 (trade name, manufactured by Arch Chemicals, Inc.)

Dyes with “Reactive” in their names were classified as reactive dyes,and dyes with “Acid” in their names were classified as acidic dyes.

The maximum absorption wavelength of a dye was measured in an aqueoussolution containing 10 ppm of the dye with a double-beamspectrophotometer U-3300 (trade name, manufactured by HitachiHigh-Technologies Corporation) using a quartz cell with an optical pathlength of 10 mm. Spectra of some dyes measured in this way are shown inthe FIGURE. The maximum absorption wavelength of a dye can be measuredeven in an ink composition in which the dye is dissolved. Depending onthe concentration of the dye, the ink composition can be diluted 500- to2000-fold with water to prepare a diluted solution, which is subjectedto the measurement with the spectrophotometer.

4.2. Ink Set

The ink sets listed in Table 2 were produced. Each of the ink sets wascomposed of four types of inks: an ink 1, an ink 2, an ink 3, and an ink4. The inks 1 to 4 correspond to brown or yellow, magenta, cyan or blue,and black inks, respectively. The inks 1 in the ink sets of Examples 21to 25 correspond to the ink jet ink compositions for textile printing ofExamples 1, 2, 3, 18, and 19, respectively, except for the differentcoloring material concentration (5% by mass). The ink 1 in the ink setof Comparative Example 6 corresponds to the ink jet ink composition fortextile printing of Comparative Example 1 except for the differentcoloring material concentration (5% by mass). The ink 1 in the ink setof Comparative Example 7 corresponds to the ink jet ink composition fortextile printing of Comparative Example 5 except for a single coloringmaterial (C.I. Acid Yellow 79) with a different coloring materialconcentration (5% by mass). The inks 2 to 4 in each of the ink sets weredifferent in the type (Table 2) and concentration (5% by mass) ofcoloring material from the ink jet ink composition for textile printingof Example 1.

TABLE 2 Example Comparative example 21 22 23 24 25 6 7 Ink componentsInk 1 C.I. Reactive C.I. Reactive C.I. Reactive C.I. Acid C.I. Acid C.I.Reactive C.I. Acid of ink set Orange 35 Orange 12 Orange 99 Brown 298Orange 56 Yellow 2 Yellow 79 Ink 2 C.I. Reactive C.I. Reactive C.I.Reactive C.I. Acid C.I. Acid C.I. Reactive C.I. Acid Red 31 Red 31 Red31 Red 289 Red 289 Red 31 Red 289 Ink 3 C.I. Reactive C.I. Reactive C.I.Reactive C.I. Acid C.I. Acid C.I. Reactive C.I. Acid Blue 15 Blue 15Blue 15 Blue 112 Blue 112 Blue 15 Blue 112 Ink 4 C.I. Reactive C.I.Reactive C.I. Reactive C.I. Acid C.I. Acid C.I. Reactive C.I. Acid Black39 Black 39 Black 39 Black 172 Black 172 Black 39 Black 172 EvaluationTextile to be Hue angle ∠h° A A A — — D — results of light printed ofprinted textile fastness 100% cotton 15 to 80 degrees Textile to be A AA — — C — printed Viscose Textile to be A B B A A D D printed SilkTextile to be A B B A B D D printed Wool Textile to be — — — A B — Cprinted PA elastomer

Part of the dyes in Table 2 are as follows:

C.I. Reactive Blue 15 maximum absorption wavelength: 672 nm

C.I. Reactive Black 39 maximum absorption wavelength: 610 nm

C.I. Acid Blue 112 maximum absorption wavelength: 633 nm

C.I. Acid Black 172 maximum absorption wavelength: 573 nm

4.3. Preparation of Pretreatment Composition

1. Method for Preparing Pretreatment Liquid from Reactive Dye

Five parts by mass of polyoxyethylene diisopropyl ether (oxyethylene=30mol), 5 parts by mass of etherified carboxymethylcellulose, 100 parts bymass of urea (hydrotropic agent), and 10 parts by mass of sodiumm-nitrobenzenesulfonate were well mixed and then added in small portionsto 1000 parts by mass of ion-exchanged water while stirring at 60° C.for 30 minutes. Subsequently, 30 parts by mass of sodium carbonate(alkaline agent) was added to the solution while stirring. Afterstirring for 10 minutes, the solution was filtered through a membranefilter with a pore size of 10 μm to produce a pretreatment composition.

2. Method for Preparing Pretreatment Liquid from Acidic Dye

A pretreatment liquid for acidic dye was prepared in the same manner asin the preparation of a pretreatment liquid for reactive dye except thatsodium m-nitrobenzenesulfonate was not added and that the alkaline agentsodium carbonate was replaced by ammonium sulfate.

4.4. Evaluation Method

4.4.1. Evaluation of Hue Angle of Printed Textile

For the ink jet ink compositions for textile printing of Examples 1 to20 and Comparative Examples 1 to 5, the hue angles ∠h° of printedtextiles were evaluated as described below.

A pretreatment composition prepared as described above was applied to atextile (100% cotton, viscose, silk, wool, or PA elastomer) with adegree of whiteness L* in the range of 85 to 95 and was dried bypressing the textile with a mangle at a pickup rate of 80%. A cartridgeof an ink jet printer PX-G930 (manufactured by Seiko Epson Corporation)was filled with an ink jet ink composition for textile printing preparedas described above. The ink jet ink composition for textile printing wasapplied to a pretreated textile at a resolution of 1440 dpi×720 dpi torecord (print) an image. The amount of ink landed was 23 mg/inch².

The textile on which the image was recorded was subjected to steaming at102° C. for 10 minutes, was then washed with an aqueous solutioncontaining 0.2% by mass of Laccol STA (manufactured by Meisei ChemicalWorks, Ltd., surfactant) at 90° C. for 10 minutes, and was dried toproduce an evaluation sample. The hue angle ∠h° of the evaluation samplewas determined according to JIS Z 8722: 2009 and was rated according tothe following criteria. The degree of whiteness L* was measured withSpectrolino (a colorimeter manufactured by X-RITE, measurementconditions: light source D65, filter D65, ϕ2 degrees). Table 3 shows theevaluation results.

A: The hue angle ∠h° ranged from 20 to 75 degrees.

B: The hue angle ∠h° was 15 degrees or more and less than 20 degrees ormore than 75 degrees and 80 degrees or less.

C: The hue angle ∠h° was less than 15 degrees or more than 80 degrees.

4.4.2. Evaluation of Light Fastness

The light fastness of the ink jet ink compositions for textile printingof Examples 1 to 20 and Comparative Examples 1 to 5 was evaluated asdescribed below.

The evaluation samples prepared in “4.4.1. Evaluation of Hue Angle ofPrinted Textile” were subjected to ISO 105 B02 and were evaluatedaccording to the following criteria. Table 3 shows the evaluationresults. In this evaluation, although color fading is examined todetermine fastness, and the hue angle is not directly measured, at leastdiscoloration can be assessed.

A: Light fastness of grade 5 or higher

B: Light fastness of grade 4 or higher and lower than grade 5

C: Light fastness of grade 3 or higher and lower than 4

D: Light fastness of lower than grade 3

E: Ineligible because the printed textile had a hue angle ∠h° outsidethe range of 30 to 65 degrees.

4.4.3. Evaluation of Color Developability (Color Density)

Evaluation samples were prepared in the same manner as in “4.4.1.Evaluation of Hue Angle of Printed Textile” except that printing wasperformed at a resolution of 1440 dpi×720 dpi on a textile (in the caseof reactive dye: 100% cotton, in the case of acidic dye: silk). Colordevelopability was evaluated with a colorimeter (trade name Spectrolino,manufactured by X-RITE) with respect to the optical density (OD) (colordensity: the sum of the OD of a yellow component and the OD of a magentacomponent) of an image. The color developability of the image was ratedon the basis of OD. The evaluation criteria are described below. Table 3shows the evaluation results.

A: OD of 2.7 or more

B: OD of 2.5 or more and less than 2.7

C: OD of 2.3 or more and less than 2.5

D: OD of less than 2.3

4.4.4. Evaluation of Recoverability from Long-Term Clogging

A cartridge of an ink jet printer PX-G930 (manufactured by Seiko EpsonCorporation) was filled with an ink jet ink composition for textileprinting. After filling, a nozzle check pattern was printed to check forsufficient filling and no nozzle clogging, and then the head wasreturned to the home position (that is, the head nozzles were coveredwith a head cap) and was left to stand for one week in a 35° C./40% RHenvironment. After left to stand, the nozzle check pattern was printedto check for the ejection state of the nozzles, thereby evaluating theink composition in terms of recoverability from long-term clogging ofthe ink jet head. The evaluation criteria are described below. Table 3shows the evaluation results.

A: The ink composition was normally ejected from all the nozzles afterone cleaning operation.

B: The ink composition was normally ejected from all the nozzles aftertwo to five cleaning operations.

C: The ink composition was normally ejected from all the nozzles aftersix to ten cleaning operations.

D: The ink composition was normally ejected from all the nozzles afterat least 11 cleaning operations, or there was a nozzle from which theink composition was not normally ejected even after at least 11 cleaningoperations.

4.4.5. Evaluation of Continuous Ejection Stability

A cartridge of an ink jet printer PX-G930 (manufactured by Seiko EpsonCorporation) was filled with an ink jet ink composition for textileprinting. Continuous solid printing was performed on 1000 A4 plain papersheets. The average number of sheets continuously printable withoutcleaning operation was determined and evaluated by the following testmethod and according to the following criteria. Table 3 shows theevaluation results.

Test method (1): Printing is interrupted when printing failure(irregularity, missing, or bending of dots) occurs, and is recovered bycleaning operation. If recovery requires multiple cleaning operations,the multiple cleaning operations are counted as one failure.

Test method (2): If printing is interrupted by running out of ink in theink cartridge, or if printing failure clearly results from running outof ink, the failure is not counted, and printing is restarted after theink cartridge is immediately replaced.

Evaluation Criteria

A: The average number of continuously printed sheets was 80 or more.

B: The average number of continuously printed sheets was 40 or more andless than 80.

C: The average number of continuously printed sheets was 20 or more andless than 40.

D: The average number of continuously printed sheets was less than 20.

TABLE 3 Comparative Example example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 1516 17 18 19 20 1 2 3 4 5 pH of composition 7.8 7.8 7.8 7.8 7.8 7.8 7.8 78.8 6.5 7.8 7.8 11 5.5 7.8 7.8 7.8 8.1 8.1 8.1 7.8 7.8 7.8 7.8 7.8Evaluation Hue angle of A A A A A A A A A A A A A A A A A A A A C B A AA results printed textile Light fastness: A A A A A A A A A A A A A A AA A — — — E D A A — 100% cotton Light fastness: A A A A A A A A A A A AA A A A A — — — E D A A — Viscose Light fastness: A B B A A A A A A A AA A A A A A A A A E D A A D Silk Light fastness: A B B A A A A A A A A AA A A A A A B A E D A A D Wool Light fastness: — — — — — — — — — — — — —— — — — A B A — — — — D PA elastomer Color A A A A A A A A A A B A B B AA A A A B D C D D C developability (OD) Recoverability A A A A A A A A AA A B A A B B B A A A B B D D B from long-term clogging Continuous A A AA A A A A A A A B A A B B B A A A B B D D B ejection stability4.4.6. Evaluation of Ink Set

The light fastness of the ink sets of Examples 21 to 25 and ComparativeExamples 6 and 7 in Table 2 was evaluated as described below. The lightfastness of the ink sets was evaluated in the same manner as in theevaluation of the light fastness of the ink jet ink compositions fortextile printing except that the ink sets were used to print an imagewhile the amount of ink landed was controlled at a resolution of 1440dpi×720 dpi or 720 dpi×720 dpi such that the hue angle ∠h° of theprinted image ranged from 15 to 80 degrees. Printing was performed on a100% cotton textile and viscose, silk, wool, an PA elastomer textiles.4.5. Evaluation Results

The results of the ink jet ink compositions for textile printing showthat the use of a dye with a hue angle ∠h° in the range of 20 to 75degrees as defined by the CIELAB color space on a recording medium and5% to 30% by mass of a cyclic amide that is liquid at normal temperatureand that has a normal boiling point in the range of 190° C. to 260° C.can produce a color with a hue angle ∠h° in the range of 20 to 75degrees with high color developability in printed textiles without colormixing of different colors, and can reduce the temporal hue change(higher light fastness).

This indicates that high color developability in printed textiles can beachieved by the ink jet ink composition including 5% to 30% by mass of acyclic amide with a normal boiling point in the range of 190° C. to 260°C., the cyclic amide enabling a sufficient amount of dye to be dissolvedin the ink jet ink composition. The results of the examples proved thata color with a hue angle ∠h° in the range of 20 to 75 degrees can beproduced without color mixing of different colors and that the temporalhue change can therefore be greatly reduced (light fastness).

By contrast, in Comparative Example 1, in which the dye with a hue angle∠h° outside the range of 15 to 80 degrees was used, printing with apredetermined hue angle could not be performed. Comparative Example 2had poor light fastness due to color mixing. Comparative Examples 1 and2 had poor recoverability from long-term clogging and ejection stabilityprobably because the use of Reactive Yellow 2 and Reactive Red 31 ascoloring materials and the excessive addition of 18% by mass of thealkyl polyol tended to increase the viscosity. Although the detailedmechanism is not clear at present, the combination of the type and/oradditive amount of coloring material and alkyl polyol probably changesthe tendency to increase viscosity during water evaporation.

Comparative Example 3 had poor color developability probably due to thelow nitrogen-containing cyclic compound content. Comparative Example 4shows that the addition of more than 30% by mass of 2-pyrrolidonereduced color developability. This probably results from increasedpenetrability of the ink to the textile. Comparative Example 4 also hadvery low recoverability from long-term clogging and ejection stabilityprobably because impurities from a member of the ink passage weredissolved in the ink and were precipitated as foreign matter.Comparative Example 5, in which the acidic dye was used, shows that theaddition of more than 30% by mass of 2-pyrrolidone reduced colordevelopability.

Examples show that the different types of dyes in Examples 2 and 3resulted in a slightly different light fastness, and RO35 provided thebest results. The results of Examples 13 and 14 show that a pH outsidethe range of 6 to 10 resulted in a slight decrease in colordevelopability. This is probably due to decreased reactivity of the dye.Example 4 shows that the use of three types of dyes did not reduce lightfastness. This is probably due to the addition of a sufficient amount ofC.I. Reactive Orange 35. This shows that if the hue of a textile printedonly with C.I. Reactive Orange 35 requires fine tuning, the addition ofapproximately 1% by mass of another dye (C.I. Reactive Orange 12, C.I.Reactive Orange 99) can maintain the light fastness level.

The results of Examples 15 and 16 show that the addition of an amount ofalkyl polyol outside the range of 10% to 25% by mass tended to reducerecoverability from long-term clogging and/or continuous ejectionstability. This is probably because the addition of less than 10% bymass of the alkyl polyol in Example 15 was insufficient for moistureretention and accelerated drying. The addition of more than 25% by massof the alkyl polyol in Example 16 probably increased the viscosityduring drying. Example 17 shows that the addition of an alkyl polyolwith a high boiling point tended to reduce recoverability from long-termclogging and/or continuous ejection stability. This is also probably dueto the increase in viscosity.

The results in Table 2 show that the ink sets of Examples had betterlight fastness (a smaller temporal hue change) than Comparative Examples6 and 7, which provided a composite ink containing multiple types ofdyes or a brown hue produced by combining inks of different hues.

The invention is not limited to the embodiments described above, andvarious modifications may be made therein. For example, the inventionincludes substantially the same constitutions as those described in theembodiments (for example, constitutions with the same functions,methods, and results, or constitutions with the same objects andadvantages). The invention also includes constitutions in whichunessential portions of the constitutions described in the embodimentsare substituted. The invention also includes other constitutions thathave the operational advantages of the constitutions described in theembodiments and other constitutions with which the same objects can beachieved. The invention also includes constitutions in which theconstitutions described in the embodiments are combined with knowntechniques.

The entire disclosures of Japanese Patent Application No. 2016-255835,filed Dec. 28, 2016 and Japanese Patent Application No. 2017-147981,filed Jul. 31, 2017 are expressly incorporated by reference herein.

What is claimed is:
 1. An ink jet ink composition for textile printing,comprising: a dye; 10% to 25% by mass of an alkyl polyol with a normalboiling point in the range of 180° C. to 260° C.; and 7% to 15% by massof a cyclic amide that is liquid at normal temperature and has a normalboiling point in the range of 190° C. to 260° C., wherein a hue angle∠h° defined by a CIELAB color space on a recording medium ranges from 15to 80 degrees.
 2. The ink jet ink composition for textile printingaccording to claim 1, wherein the hue angle ∠h° defined by a CIELABcolor space on a recording medium ranges from 20 to 75 degrees.
 3. Theink jet ink composition for textile printing according to claim 1,wherein the dye has a maximum absorption wavelength in the range of 350to 450 nm.
 4. The ink jet ink composition for textile printing accordingto claim 1, wherein the dye is at least one of C.I. Reactive Orange 35,C.I. Reactive Orange 12, C.I. Reactive Orange 99, C.I. Acid Brown 298,and C.I. Acid Orange
 56. 5. The ink jet ink composition for textileprinting according to claim 1, wherein the dye content ranges from 3% to15% by mass.
 6. The ink jet ink composition for textile printingaccording to claim 1, wherein the ink jet ink composition for textileprinting has a pH in the range of 6 to
 10. 7. An ink set comprising theink jet ink composition for textile printing according to claim
 1. 8. Anink set comprising the ink jet ink composition for textile printingaccording to claim
 2. 9. An ink set comprising the ink jet inkcomposition for textile printing according to claim
 3. 10. An ink setcomprising the ink jet ink composition for textile printing according toclaim
 4. 11. An ink set comprising the ink jet ink composition fortextile printing according to claim
 5. 12. An ink set comprising the inkjet ink composition for textile printing according to claim
 6. 13. Arecording method comprising: a pretreatment process of applying apretreatment composition containing at least one of an alkaline agent,an acid, and a hydrotropic agent to a textile; and a printing process ofapplying the ink jet ink composition for textile printing according toclaim 1 to the textile.
 14. A recording method comprising: apretreatment process of applying a pretreatment composition containingat least one of an alkaline agent, an acid, and a hydrotropic agent to atextile; and a printing process of applying the ink jet ink compositionfor textile printing according to claim 2 to the textile.
 15. Arecording method comprising: a pretreatment process of applying apretreatment composition containing at least one of an alkaline agent,an acid, and a hydrotropic agent to a textile; and a printing process ofapplying the ink jet ink composition for textile printing according toclaim 3 to the textile.
 16. A recording method comprising: apretreatment process of applying a pretreatment composition containingat least one of an alkaline agent, an acid, and a hydrotropic agent to atextile; and a printing process of applying the ink jet ink compositionfor textile printing according to claim 4 to the textile.
 17. Arecording method comprising: a pretreatment process of applying apretreatment composition containing at least one of an alkaline agent,an acid, and a hydrotropic agent to a textile; and a printing process ofapplying the ink jet ink composition for textile printing according toclaim 5 to the textile.
 18. A recording method comprising: apretreatment process of applying a pretreatment composition containingat least one of an alkaline agent, an acid, and a hydrotropic agent to atextile; and a printing process of applying the ink jet ink compositionfor textile printing according to claim 6 to the textile.